US2983692A - Preparation of expandable ethylenically unsaturated polymer particles and cellular product therefrom - Google Patents

Preparation of expandable ethylenically unsaturated polymer particles and cellular product therefrom Download PDF

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US2983692A
US2983692A US394230A US39423053A US2983692A US 2983692 A US2983692 A US 2983692A US 394230 A US394230 A US 394230A US 39423053 A US39423053 A US 39423053A US 2983692 A US2983692 A US 2983692A
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Alelio Gaetano F D
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16Making expandable particles
    • C08J9/18Making expandable particles by impregnating polymer particles with the blowing agent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/13Cell size and distribution control while molding a foam
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/918Physical aftertreatment of a cellular product

Description

Patented May 9, 1961 PREPARATIQN OF EXPANDABLE E'IHYLENICAL- LY UNSATURATED POLYMER PARTICLES AND CELLULAR PRODUCT 'I'HEREFROM Gaetano F. DAlelio, Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware No Drawing. Filed Nov. 24, 1953, Ser. No. 394,230

9 Claims. (Cl. 260-25) This application is concerned with a new process for the preparation of cellular polymers. More particularly, it is concerned with the method for the preparation of cellular polymers utilizing as starting materials polymeric vinyl aryl compounds and their copolymers. In an important aspect of the invention, it is concerned with the production of cellular polymers from polymeric materials produced by suspension polymerization. A particular feature of the process of this invention is the introduction of a normally liquid expanding agent into an aqueous suspension of a polymeric vinyl aryl compound whereby there are produced free-flowing beads containing the eX- panding agent which upon heating produce cellular polymeric structures.

In the past, the production of cellular polymeric structures has been attained by a variety of methods such as the introduction of a normally gaseous expanding agent into the polymeric material under pressure followed by release of pressure whereby cellular material is produced; the physical admixture by such means as milling or masticating of a polymeric material and a normally liquid expanding agent followed by suitable shaping and heating to produce a cellular structure; and the admixture of chemical blowing agents which decompose with a polymeric material followed by decomposition of said blowing agents whereby cellular structures are produced.

With the advent of suspension polymerization which has found particular applicability in the polymerization of vinylaryl compounds such as, for example, styrene, there has been made available polymeric materials in bead form which polymers are potentially useful for the production of cellular polymeric structures. However, ac-

cording to known methods these bead polymers produced in aqueous suspensions must be separated from the suspension, washed, dried, and then admixed by one of the known methods with an expanding agent for the production of cellular polymeric structures.

It has been discovered as a feature of this invention that it is possible to introduce into a stabilized aqueous suspension of polymeric particles a normally liquid expanding agent and that this agent can be integrated with said particles without causing agglomeration or precipitation of the suspended polymer particles.

This invention comprises a process for the production of polymeric particles capable of being expanded to produce a cellular polymeric structure comprising forming an aqueous suspension of particles of a polymer derived from an ethylenically unsaturated hydrocarbon monomer, said suspension being stabilized by an inorganic suspending agent preferably in combination with an anionic sur- 2 face-active agent, adding thereto a normally liquid expanding agent, maintaining said expanding agent in contact with said suspension until said agent is integrated with said polymer particles and separating said particles from said aqueous suspension. Thereafter, the polymer particles can be expanded individually to produce discrete cellular particles or can be placed in a mold and then heated to at least the incipient softening point of the polymeric material whereby the discrete polymer particles coalesce to produce an integral cellular polymeric structure. As used herein the term polymer is intended to embrace both homoand co-polymers.

The invention is applicable to a variety of homopolymers and copolymers derived from hydrocarbon vinyl monomers. Such monomers are, for example, ethylene, styrene, nuclear dimethyl styrenes, isobutylene, vinyl naphthalene, etc.

Copolymers of hydrocarbon vinyl monomers such as, for example, styrene and butadiene, styrene and a-methyl styrene, styrene, butadiene and rat-methyl styrene, styrene and isobutylene, styrene and dimethyl styrene, isobutylene and butadiene can be treated according to the process of this invention to produce free-flowing particles capable of being expanded to produce a cellular polymeric structure. Further, the invention is applicable to particles of blends of polymers such as, for example, impact polystyrene which is an admixture of polystyrene with an elastomer, such as, for example, a styrene-butadiene copolymer.

The invention has particular utility with respect to vinyl aryl polymers, such as, for example, polystyrene and its copolymers with such monomers as butadiene, rat-methyl styrene and isobutylene.

In general, the requisites for a normally liquid expanding agent useful in this invention are that it be capable of being integrated with the particular polymeric material being treated Without so altering the characteristics of the polymer particles that agglomeration or precipitation of the particles from the suspension occurs. Further, the expanding agent should have a high volatility, that is, that it boil somewhat below the incipient softening point of the particular polymeric material in connection with which it is to be used. Aliphatic hydrocarbons boiling below the incipient softening point of the polymer with which they are to be used are useful in the process of this invention.

It has been found that petroleum ethers and certain ligroines give excellent results when used as expanding agents in a process of this invention, particularlyin connection with vinyl aryl polymers, especially polystyrene. Expanding agents boiling in the range 30-1 00 C. are useful. The preferred agents boil in the range 35-40" 0, although excellent results are obtained with agents boiling in the range 35-65 C. denoted as the pentane fraction. Other examples of normally liquid expanding agents useful herein are the petroleum ethers boiling in the range 65-72" C. denoted as the hexane fraction and the petroleum ethers boiling in the range l00 C. denoted as the heptane fraction. Similarly useful are the pure hydrocarbons boiling in the range 35-100 C. such as, for example, pentane, hexane, heptane, cyclopentane, cyclopentadiene, etc., although it is preferred for reasons of economy to utilize mixtures of such hydrocarbons as petroleum ethers.

Further, it has been observed that minor quantities of volatile solvents for the particular polymeric material being processed can be admixed with the above-described petroleum ethers to give satisfactory normally liquid expanding agents. For example, there can be admixed with petroleum ether such compounds as chloroform, carbon tetrachloride, methyl ethyl ketone, toluene, etc. It is preferred that the minor quantities of such solvents not exceed 20% by Weight of the normally liquid expanding agent. The criterion as to the upper limit of the amount of such volatile solvent to be admixed with the abovedescribed aliphatic hydrocarbon expanding agents is that the resulting mixture is not a complete solvent for the particular polymer with which it is to be used.

As used herein the term normally liquid expanding agents embraces aliphatic hydrocarbons boiling in the range of "approximately 35-100 C. and mixtures thereof with volatile solvents in such amounts that the resulting mixture is not a solvent for the polymer.

It has been observed that by the use of normally liquid expanding agents in amounts of from approximately 5 to 30 parts per 100 parts of free-flowing expandable beads, that is, polymer plus expanding agent, expanded polymeric structures are produced. Particularly good results are obtained in the range of above 7 parts as before described. The preferred amount of normally liquid expanding agent is 10 parts per 90 parts polymeric material.

The preferred class of dispersing agents utilizable herein are the difficultly-soluble phosphates described in Grim 2,594,913, that is, those phosphates which are dithcultly soluble in water and contain for each phosphate group at least three equivalents of a metal, the carbonate of which is at most only slightly soluble in water. Of these phosphates particularly desirable results are obtained with the calcium and magnesium phosphates, particularly those having an apatite structure, for example, hydroxy apatite, 3Ca (PO .Ca(OH) Particularly useful are those phosphates which are comprised of particles predominantly in the range 0.2- 0.005 micron. Other dispersing agents which find utility are, for example, zinc oxide, calcium carbonate, calcium fluoride, bentonite, talc, kaolin, kieselguhr, aluminum oxide, barium sulfate, magnesium carbonate, ferric carbonate, magnesium silicate, etc. dispersibility of these agents vary widely, a principal difference residing in the amount of polymeric material which can be present with relation to the water in the aqueous suspension without agglomeration or precipitation occurring. While lower polymer/Water ratios must be utilized with the less effective suspending agents, the preferred phosphate suspending agents can be used with a polymer/water ratio as high as approximately 2.33/1. In connection with the treatment of polystyrene utilizing a tricalcium phosphate composed of approximately equal parts of tricalcium phosphate mono'hydrate and hydroxy apatite in combination with sodium dodecylbenzene sulfonate, excellent results have been obtained with a poly met/water ratio of approximately 1.35/1.

Although it is preferred to utilize the combination of a phosphate suspending agent and an anionic surface-active agent, it will be realized that the suspending agent can be utilized alone. However, since their ability to suspend the polymeric particles is augmented by combination with the anionic surface-active agents, the use of the suspending agent alone requires the use of lower polymer/water ratios.

As described above, the process of this invention comprises as one of its steps maintaining the normally liquid expanding agent in contact with the suspended polymer until the expanding agent is integrated with the polymeric material. It has been observed that the time required for this to occur varies widely and depends upon such factors as the temperature and pressure of the system, the polymer being treated, the particular normally liquid expanding agent utilized, and the relative amounts of It will be realized the polymer and expanding agent utilized. For example, utilizing 70 parts polystyrene and 30 parts petroleum ether boiling in the range 35-65 C. at atmospheric pressure and 20 C., there were obtained at the end of 60 hours polymer particles containing the petroleum ether which upon heating yielded cellular polystyrene.

In the treatment of polystyrene, it is preferred to utilize a polymer/ expanding agent ratio of 90/ 10 and to maintain the system at approximately 90 C. for from approximately 2 to 4 hours. The pressure of this system ranges as high as approximately 65 pounds per square inch gauge. It is to be noted that increased pressure is desirable in this system since it tends to decrease the time required for the integation of the normally liquid expanding agent with the polymeric material.

It has been observed that treatment time of 2 hours at 70 C. for parts polystyrene and 20 parts petroleum ether boiling in the range 35-65 C. yields free-flowing beads which are capable of being expanded to produce a cellular structure. Further, one-hour treatment at 70 C. of 70 parts polystyrene and 30 parts of the abovedescribed petroleum ether yields satisfactory free-flowing expandable beads.

Although it is not necessary, it is preferred that the suspending agent be removed from the polymer particles. When utilizing the phosphate suspending agents, this can be accomplished easily by washing the polymer particles with dilute hydrochloric acid.

The aqueous dispersions to which are added the normally liquid expanding agents can be formed by adding the desired amount of suspending agent, for example, tricalcium phosphate, hydroxy apatite or magnesium phosphate with or without an anionic surface-active agent to the desired amount of water, stirring and adding there to the polymer particles. The norrnally liquid expanding agent is then added, the system closed and the temperature raised to the desired point for the desired period of time. Although it is not necessary, it is preferred that the suspension be agitated such as, for example, by stirring since this not only reduces the time required to complete integration of the expanding agent with the polymeric material but assures uniformity of treatment.

Alternately, and in particular, in connection with a liquid monomer, such as, for example, styrene, the polymerization can be eifected in suspension as described in Grim 2,594,913. Thereafter, without cooling the suspension of the polystyrene beads, there can be added under pressure the desired amount of the normally liquid expandlng agent such as petroleum ether and the suspension stirred for preferably from 2 to 4 hours to produce free-flowing polymeric beads having integrated therein the normally liquid expanding agent.

It has been noted in connection with polystyrene that particularly excellent results are obtained in the production of cellular polymer structures when polystyrene beads of a size between 10-30 mesh are utilized. Smaller beads and even polymer particles such as are produced by emulsion polymerization can be utilized. Further, granules or pellets of a size normally utilized for moldmg purposes can be treated by the process of this invention to yield polymer particles capable of being expanded to produce a cellular structure. However, beads in the above-recited size range are preferred for general purpose use.

The cellular polymeric structures are obtained by expansion of the normally liquid expanding agent integrated with the polymeric material. This can be accomplished by various methods of heating such as, for example, with air or steam.

The products of varying density can be obtained by varying the quantity of expandable beads placed in a mold and expanded by the introduction of steam or introduction of Water followed by heating of themold to produce steam. For example, when approximately 7-8 percent of the mold volume is filled with expandable polystyrene beads, the mold having vent means therein closed and steam thereafter introduced, there is obtained a cellular polystyrene structure of a density of approximately 2.2

pounds per cubic foot which structure has small voids.

By the above expansion there can be obtained desirable polymeric structures having densities as low as approximately 1 pound per cubic foot, that is, 0.016 specific gravity. These products have low thermal conductivity and good compressive and impact strengths.

Discrete particles of cellular structure can be obtained, for example, by dropping the beads into hot Water and allowing expansion to take place or by heating in air.

.Thus, by varying the time of heating products of different densities are obtained. For example, Table I illustrates the variance of the density of the product with time of immersion in water at 95 C. of expandable polystyrene beads containing 90 parts polystyrene and parts pentane fraction petroleum ether.

TABLE I Time of exposure: Density cubic ft.) 0 32.8 10 seconds 22.1 30 seconds 9.5 60 seconds 4.2 120 seconds 2.6 1 hour 1.5

Table II illustrates treatment of similar beads in an oven at 120 C. for varying times.

As used herein the terms parts and percentages are parts and percentages by weight unless otherwise specified.

The invention is illustrated by but not restricted to the following preferred embodiments.

Example I To a kettle equipped with a stirrer 354 parts of deionized water are admixed with 3.72 parts of a tricalcium phosphate composed of approximately 50 parts tricalcium phosphate monohydrate and 50 parts hydroxy apatite and the system purged with nitrogen. There is then added with nitrogen purging 428 parts styrene containing 0.868 part benzoyl peroxide and 0.189 part tertiary-butyl perbenzoate. Stirring is commenced and there is added 0.0164 part Nacconol sodium dodecylbenzene sulfonate. The system is heated over a period of approximately 1% hours to approximately 90 C. and held there for approximately 6 /2 hours. Thereafter the temperature is raised over a period of approximately hour to 115 C. and held there for 3 hours after which the temperature is reduced to 90 C. There is added under pressure 47.6 parts petroleum ether boiling in the range 3565 C. and the system maintained at 90 C. at approximately 60-70 p.s.i. for 4 hours. The suspension is cooled, the beads separated therefrom by centrifuging and the beads washed with dilute hydrochloric acid. There are obtained freeflowing expandable polystyrene beads containing petroleum ether. These expandable beads may be used in a wet condition or dried to remove the small amounts of surface water attached to them.

' to produce an integral cellular structure.

A mold having vent means therein is filled approximately 8 percent full of the heads, the mold closed and steam introduced therein. After 10 minutes the addition of steam is discontinued, the mold opened and the product removed. There is obtained cellular polystyrene having small voids and a density of approximately 2.2 pounds per cubic foot.

When approximately 1 part hydroxy apatite is used in place of the tricalcium phosphate in the foregoing example, substantially identical results are obtained. Similarly, there can be substituted for the tricalcium phosphate the various phosphates and for the Nacconol sodium dodecylbenzene sulfonate the various anionic surface-active agents described in Grim 2,594,913, particularly in amounts of from 0.0020.004 part/100 parts suspension.

Example [I To a suitable vessel equipped with a stirrer there is added 768 parts water and 16.8 partsof the tricalcium phosphate of Example I. Stirring is commenced and there is added 192 parts polystyrene beads, approximately of which are of a size in the range 10-30 mesh. There is added 0.048 part sodium dodecylbenzene sulfonate and 21.3 parts petroleum ether boiling in the range 35-65 C. are added. The system is closed and the temperature is raised over a period of approximately 1% hours to C. and held there for approximately 4 hours. The suspension is then cooled. One-half the charge is centrifuged to give free-flowing polystyrene beads having integrated therein the petroleum ether which upon molding as described in Example I yield cellular polystyrene.

The remaining one-half of the charge .is acidified to a pH of approximately 2.0 with hydrochloric acid and is centrifuged and the beads washed with cold Water. There are obtained free-flowing polystyrene beads having integrated therein petroleum ether which, upon molding as described in Example I, yield cellular polystyrene.

The beads from the portion of the charge which is not acidified before centrifuging has some suspending agent admixed therewith. The cellular products derived from these heads have less mechanical strength than do the beads from which the suspending agent has been removed by the acid treatment.

'When approximately 4 parts hydroxy apatite are used in place of the tricalcium phosphate in the foregoing example, substantially identical results are obtained. Similarly, there can be substituted for the tricalcium phosphate the various phosphates and for the Nacconol sodium dodecylbenzene sulfonate the various anionic surface-active agents described in Grim 2,594,913.

Example III Various suspensions composed of 80 parts Water and 20 parts polystyrene beads are prepared using 1.75 parts of the tricalcium phosphate described in Example I and 0.005 part Nacconol sodium dodecylbenzene sulfonate. The amounts and compositions of the normally liquid expanding agent are indicated in the below set out Table III. These suspensions are placed in a closed system and agitated while being maintained at approximately 90 C. for 4 hours. There are obtained in each instance freeflowing beads, which upon expansion produce cellular polystyrene. It is observed that when less than 5 parts expanding agent per parts polymeric materials are utilized, the results obtained upon heating the beads are not uniform and that in some instances there is failure Additionally, as the amount of expanding agent is increased above ap proximately 15 parts per 85 parts polymeric particles, there is a tendency towards the production of cellular structures having medium or large sized voids.

7 TABLE 111 Normally Liquid Expanding Agent Polystyrene I-Iethylethyl ketone... Carbon tetrachloride Trichlorethylene Toluene Parts Petroleum Ether Additive Type Parts Type Parts 94 Pentano- 4. 3 1. 7 .-.-.do 4. 7 1.3 5.1 0. 9 5. 4 0.6 5. 6 0. 4 5. 7 2. 3 6. 3 1. 7 6. 9 1.1 7.1 O. 9 7. 4 O. 6 7. 1 2. 9 7. 9 2. 1 8. 6 1. 4 8. 9 1.1 9. 3 0. 7 8. 6 3. 4 9. 4 2. 6 10. 3 1. 7 10. 7 1. 3 11.1 0.9 10 a 11 3 12 2 NoTE.Pentane (B.P. 3758 0.). Eexane (31?. 60-67 0.).

Heptaue (15.1. 90-95" 0.).

Example IV The procedure of Example III is duplicated except that for the normally liquid expanding agents there used there are substituted the below indicated petroleum others as expanding agents. Cellular structures having small voids are obtained upon expansion in all instances except Wherein less than parts expanding agent is used, that is, with 98 parts polystyrene and 2 parts pentane fraction, 97 parts polystyrene and 3 parts hexane fraction and 97 parts polystyrene and 3 parts heptane fraction, when no expansion is observed. In the instance wherein 85 parts polystyrene and 15 parts pentane fraction is used, medium voids are noted.

TABLE IV Petroleum Ether Polystyrene Type Parts 0 3 94-. o 6 97.. Heptandk 3 94.. .do 6 90.. 1 -410 l0 on 7 93 ifIicpvsne 1 1 See Table III footnote Example V A suspension composed of 90 parts each of water and polystyrene heads is prepared using as a suspending agent 0.9 part hydroxy apatite, said apatite being comprised of particles predominantly of the size in the range 6.2-0.005 micron. There is added 10 parts pentane fraction and the suspension is stirred While it is heated to 90 C. where it is maintained while stirring for 2-4 hours. The suspension is cooled, the beads separated therefrom by centrifuging and the beads washed in dilute hydrochloric acid. There are obtained free-flowing expandable beads containing petroleum ether. 7

A mold having vent means therein is filled approximately 12-15% full of heads, the mold closed and steam introduced therein. After 2 to 1 0 minutes the addition of v Example VI A suspension of parts water and 10 parts polystyrene is prepared using as a suspending agent One part magnesium trisilicate. There is added 1.1 parts pentane fraction and the suspension stirred while it is heated to and maintained at 90 C. for approximately 2-4 hours. There are obtained free-flowing expandable polystyrene beads containing petroleum ether therein. Upon expansion as described in Example V substantially similar results are obtained. When 0.5 part talc is substituted in the foregoing procedure for the magnesium trisilicate there used, substantially similar results are obtained. Similarly, when there is substituted for the magnesium trisilicate utilized in the foregoing procedure approximately equal parts of zinc oxide, calcium carbonate, aluminum oxide, barium sulfate, and magnesium and ferric carbonates, substantially similar results are obtained. Further, equal parts of bentonite, kaolin, and kieselguhr can be substituted for the magnesium trisilicate to give satisfactory results.

Example VII Polystyrene beads are prepared by heating and stirring at approximately 90 C. an aqueous suspension of 50 parts water, 50 parts styrene and 0.5 part hydroxy apatite of a particle size described in Example V, said styrene containing 0.5% benzoyl peroxide (based on the styrene). Heating and stirring is carried out for approximately 5-6 hours after which time there is introduced under pressure 5.5 parts pentane fraction of petroleum ether and the stirring continued for 2-4 hours. The suspension is cooled and the beads separated therefrom by centrifuging after which they are washed with dilute hydrochloric acid. There are obtained free-flowing expandable polystyrene beads containing petroleum ether therein. Upon molding as described in Example I there is obtained an integral cellular polystyrene structure.

Example VIII Particles of a co-polymer of parts styrene and 5 parts butadiene are suspended in an aqueous suspension and treated with petroleum ether as described in Example I. There are obtained free-flowing expandable polymeric particles which upon expansion as described in Example I produce a cellular polymeric structure. Particles of a copolymer of 95 parts styrene and 5 parts alpha-methylstyrene can be substituted in the foregoing procedure for the styrene-butadiene copolymer there used. There are obtained free-flowing expandable polymer beads which upon expansion produce a cellular polymeric structure.

Example IX Polyethylene particles are treated in an aqueous suspension With petroleum ether as described in Example I. There are obtained free-flowing expandable polyethylene particles containing petroleum ether therein. Upon expansion with steam superheated to approximately 120 0., according to the procedure outlined in Example I, there is obtained polyethylene having a cellular structure.

Example X ether are separated from the suspension by centrifuging.

Polymer Petroleum Run No. Particles Ether Parts Parts In each instance there are obtained expandable polymer particles. Upon molding (as described in Example I) of beads from run No. 2 there is obtained a cellular polymeric structure having good impact strength.

The various phosphate suspending agents described in Example II can be substituted in the foregoing procedure for the tricalcium phosphate there used.

Example XI One hundred parts of a 75/25 butadiene/styrene copolymer is homogeneously admixed with 0.5 part sulfur, 1.5 part sodium diethyl dithiocarbamate and 3 parts tetraethylthiuram disulfide. The composition is formed into granules of a size normally utilized for molding purposes and suspended in an aqueous suspension and treated with petroleum ether as described in Example II.

The expandable polymer beads are expanded in a mold as described in Example I and the cellular polymer structure subjected to an open steam cure at approximately 390 F. for 7-10 seconds. There is obtained a cured cellular polymeric structure having good impact strength.

Various styrene/butadiene copolymers of styrene contents ranging as low as those usually found in GR-S rubbers can be substituted in the foregoing procedure for the copolymer there used to obtain cured cellular polymeric structures.

It will be realized that in the foregoing examples for the Nacconol sodium dodecylbenzene sulfonate there can be substituted the various anionic surface-active agents disclosed in Grim 2,594,913 and that the amounts of these various agents described as useful in that patent are useful herein.

While the invention has been described with reference to particular embodiments thereof, it Will be understood that in its broader aspects the invention is not limited thereto, but the invention may be variously embodied within the scope of the invention as set forth herein and in the appended claims.

What is claimed is:

1. A process for the production of polymeric particles capable of being expanded to produce a cellular polymeric structure comprising forming an aqueous suspension of particles of a polymer obtained by polymerizing an ethylenically unsaturated hydrocarbon monomer, said suspension being stabilized by an inorganic diflicultly water-soluble dispersing agent and an anionic surfaceactive agent, adding thereto a normally liquid aliphatic 10 hydrocarbon boiling in the range 35l00 C., maintaining said hydrocarbon in contact with said suspension until said hydrocarbon is integrated with said polymer particles and separating said particles from said aqueous suspension.

2. A process of claim 1 in which the inorganic diflicultly Water-soluble dispersing agent is hydroxy apatite and the anionic surface-active agent is sodium dodecylbenzene sulfonate.

3. A process of claim 1 in which the polymer is a mono-vinyl aryl polymer.

4. A process of claim 1 in which the polymer is polystyrene.

5. A process of claim 4 in which the diflicultly watersoluble dispersing agent is. hydroxy apatite, the anionic surface-active agent is sodium dodecylbenzene sulfonate, and the aliphatic hydrocarbon is petroleum ether of a boiling range of from 30-65 C.

6. A process of claim 4 in which said inorganic difficultly water-soluble dispersing agent is magnesium phosphate, the anionic surface-active agent is sodium dodecylbenzene sulfonate, and the aliphatic hydrocarbon is petroleum ether of a boiling range of from 30-65 C.

7. A process for the production of shaped cellular polymeric structures comprising forming an aqueous suspension of particles of a polymer obtained by polymerizing an ethylenically unsaturated hydrocarbon monomer, said suspension being stabilized by an inorganic difiicultly water-soluble dispersing agent, adding thereto a normally liquid aliphatic hydrocarbon having a boiling point below the incipient softening point of said polymer, maintaining said aliphatic hydrocarbon in contact with said suspension until said hydrocarbon is integrated with said polymer particles, separating said particles from said aqueous suspension, filling a mold with said polymer particles, heating said polymer particles to at least the incipient softening point of the polymer whereby the discrete polymer particles coalesce to produce an integral cellular polymeric structure and removing said structure from said mold.

8. A process for the production of polystyrene beads capable of being expanded to produce cellular polystyrene comprising forming an aqeous suspension of 100 parts polystyrene beads and approximately 83 parts water, said suspension being stabilized by 0.87 part tricalcium phosphate comprised of approximately equal parts of tricalcium phosphate monohydrate and hydroxy apatite and 0002-0004 part sodium dodecylbenzene s'ulfonate, adding thereto 10 parts of petroleum ether of a boiling range of 35-65 C., maintaining said petroleum ether in contact with said suspension at approximately C. for approximately l-4 hours, cooling said suspension, and separating said beads therefrom.

9. The process of claim 8 in which the beads are washed with dilute hydrochloric acid after separating from said suspension.

References Cited in the file of this patent UNITED STATES PATENTS 2,371,868 Berg et a1 Mar. 20, 1945 2,373,347 Schoenfeld Apr. 10, 1945 2,43 5,999 Dreyfus et a1 Feb. 17, 1948 2,442,940 Staudinger-et al. June 8, 1948 2,493,965 Haefele Jan. 10, 1950 2,550,503 Turnbull Apr. 24, 1951 2,556,260 Downing June 12, 1951 2,681,321 Stastny et a1 June 15, 1954 2,744,291 Stastny et al May 8, 1956

Claims (1)

  1. 7. A PROCESS FOR THE PRODUCTION OF SHAPED CELLULAR POLYMERIC STRUCTURES COMPRISING FORMING AN AQUEOUS SUSPENSION OF PARTICLES OF A POLYMER OBTAINED BY POLYMERIZING AN ETHYLENICALLY UNSATURATED HYDROCARBON MONOMER, SAID SUSPENSION BEING STABILIZED BY AN INORGANIC DIFFICULTLY WATER-SOLUBLE DISPERSING AGENT, ADDING THERETO A NORMALLY LIQUID ALIPHATIC HYDROCARBON HAVING A BOILING POINT BELOW THE INCIPIENT SOFTENING POINT OF SAID POLYMER, MAINTAINING SAID ALIPHATIC HYDROCARBON IN CONTACT WITH SAID SUSPENSION UNTIL SAID HYDROCARBON IS INTEGRATED WITH SAID POLYMER PARTICLES, SEPARATING SAID PARTICLES FROM SAID AQUEOUS SUSPENSION, FILLING A MOLD WITH SAID POLYMER PARTICLES, HEATING SAID POLYMER PARTICLES TO AT LEAST THE INCIPIENT SOFTENING POINT OF THE POLYMER WHEREBY THE DISCRETE POLYMER PARTICLES COALESEE TO PRODUCE AN INTEGRAL CELLULAR POLYMERIC STRUCTURE AND REMOVING SAID STRUCTURE FROM SAID MOLD.
US394230A 1953-11-24 1953-11-24 Preparation of expandable ethylenically unsaturated polymer particles and cellular product therefrom Expired - Lifetime US2983692A (en)

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BE532626D BE532626A (en) 1953-11-24
US394230A US2983692A (en) 1953-11-24 1953-11-24 Preparation of expandable ethylenically unsaturated polymer particles and cellular product therefrom
GB2882954A GB756654A (en) 1953-11-24 1954-10-06 Improvements in or relating to treatment of polymeric materials
FR1113827D FR1113827A (en) 1953-11-24 1954-10-15 Improvements in the processing of polymeric materials
CH332147D CH332147A (en) 1953-11-24 1954-11-12 Process for obtaining particles of polymeric materials capable of swelling under the action of heat by generating a cellular structure
ES0218623A ES218623A1 (en) 1953-11-24 1954-11-24 Method for treating polymer materials

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US3192169A (en) * 1965-01-07 1965-06-29 Kenneth W Doak Method of making expandable polymeric styrene particles
US3207712A (en) * 1961-12-08 1965-09-21 Koppers Co Inc Process for the production of expandable particles of styrene polymer
US3250730A (en) * 1962-10-15 1966-05-10 Hercules Powder Co Ltd Preparation of molded plastic articles
US3252228A (en) * 1962-04-23 1966-05-24 Lodge & Shipley Co Expander for polymeric material
US3304274A (en) * 1963-06-13 1967-02-14 Union Carbide Corp Anhydrous process for the preparation of expandable particulate styrene polymers
US3305497A (en) * 1963-04-10 1967-02-21 Diamond Alkali Co Cellular polyurethanes produced using a mixture of (a) chloroform and (b) a fluorine substituted alkane as the blowing agent
US3331899A (en) * 1964-11-30 1967-07-18 Koppers Co Inc Process and apparatus for making shaped cellular articles from expandable thermoplastic resins
US3342760A (en) * 1961-10-26 1967-09-19 Koppers Co Inc Expandable polymers
US3359130A (en) * 1963-11-12 1967-12-19 Papex Corp Double shelled foamable plastic particles
US3379799A (en) * 1965-10-20 1968-04-23 Papex Corp Method of making foamed plastics
US3386926A (en) * 1963-05-20 1968-06-04 Pechiney Saint Gobain Method of making expandable pearls of styrene copolymer
US3449268A (en) * 1966-05-31 1969-06-10 Dow Chemical Co Process for making foamable isotactic polystyrene
US3449270A (en) * 1968-05-28 1969-06-10 Dow Chemical Co Method of making foamed crystalline vinyl aromatic polymer
US3468820A (en) * 1965-01-16 1969-09-23 Basf Ag Production of particulate expandable styrene polymers
US3494879A (en) * 1966-05-23 1970-02-10 Alfred J Ackerman Preparation of free-flowing foamable polystyrene beads
US3503908A (en) * 1967-07-31 1970-03-31 Koppers Co Inc Method of making expandable polymers
US3528433A (en) * 1968-03-21 1970-09-15 Philip Morris Inc Smoking product having microreticulated filter
US3903024A (en) * 1973-10-19 1975-09-02 Arco Polymers Inc Photodegradable styrene polymer foams
US3917545A (en) * 1973-04-05 1975-11-04 Arco Polymers Inc Photodegradable styrene polymer foams containing a hydrocarbon photosensitizer
US3960787A (en) * 1971-10-25 1976-06-01 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparing foamable synthetic resin granules
US4018946A (en) * 1971-01-15 1977-04-19 Sealed Air Corporation Production of heat-expandable styrene-polymer bit-pieces
US4200679A (en) * 1973-03-16 1980-04-29 Max Klein Micro-bits of expanded flexible polyurethanes
US4207378A (en) * 1973-03-16 1980-06-10 Max Klein Expanded styrene-polymers and polyolefin micro-bits and their preparation
US4304873A (en) * 1977-09-15 1981-12-08 Max Klein Preparation of expanded flexible polyurethane foam micro-bits
EP0518140A1 (en) 1991-05-31 1992-12-16 ENICHEM S.p.A. Process for producing foamable particles of styrenic polymers
US5939180A (en) * 1994-12-14 1999-08-17 Sekisui Kagaku Kogyo Kabushiki Kaisha Thermoplastic resin foam and method of preparing the same
US5960851A (en) * 1998-08-04 1999-10-05 Brunswick Corporation Method of lost foam casting of aluminum-silicon alloys
US6263950B1 (en) 1999-03-26 2001-07-24 General Motors Corporation Lost foam casting using dimensionally self-stabilized pattern
US20060191232A1 (en) * 2005-02-25 2006-08-31 Nova Chemicals, Inc. Composite pre-formed building panels
US20060201090A1 (en) * 2005-02-25 2006-09-14 Tricia Guevara Lightweight compositions and articles containing such
WO2006102523A2 (en) 2005-03-22 2006-09-28 Nova Chemicals Inc. Lightweight concrete compositions
US20070148385A1 (en) * 2005-12-22 2007-06-28 Nova Chemicals Inc. Methods for improving the resistance of fumigant sorption in a produce container and a related produce containers
US20070148386A1 (en) * 2005-12-22 2007-06-28 Nova Chemicals Inc. Method for improving the resistance of fumigant sorption in an expandable polymer produce container and a related container
WO2007111850A2 (en) 2006-03-22 2007-10-04 Nova Chemicals Inc. Lightweight concrete compositions
US20080020156A1 (en) * 2005-08-22 2008-01-24 Nova Chemicals Inc. Labeled containers, methods and devices for making same
US20080184651A1 (en) * 2007-02-02 2008-08-07 Bowman Jay J Roof truss system
US20080227891A1 (en) * 2007-03-14 2008-09-18 Nova Chemicals Inc. Methods for making concrete compositions
US20080250739A1 (en) * 2006-11-08 2008-10-16 Nova Chemicals Inc. Foamed plastic structures
US20090011667A1 (en) * 2007-03-26 2009-01-08 Nova Chemicals Inc. Sportsboard structures
US20090081446A1 (en) * 2007-09-20 2009-03-26 Nova Chemicals Inc. Method of placing concrete
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US7536767B2 (en) 2005-05-27 2009-05-26 Prairie Packaging, Inc. Method of manufacturing a reinforced plastic foam cup
US20090162588A1 (en) * 2007-12-19 2009-06-25 Nova Chemicals Inc. Labeled containers made from expandable thermoplastic materials having improved physical properties
US7552841B2 (en) 2005-05-27 2009-06-30 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7628597B2 (en) 2005-08-22 2009-12-08 Nova Chemicals Inc. Labeled containers, methods and devices for making same
US20090313914A1 (en) * 2008-06-20 2009-12-24 Nova Chemicals, Inc.. Footer cleat for insulating concrete form
US7694843B2 (en) 2005-05-27 2010-04-13 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7704347B2 (en) 2005-05-27 2010-04-27 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7814647B2 (en) 2005-05-27 2010-10-19 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7818866B2 (en) 2005-05-27 2010-10-26 Prairie Packaging, Inc. Method of reinforcing a plastic foam cup
US20110138725A1 (en) * 2005-02-25 2011-06-16 Nova Chemicals Inc. Composite pre-formed construction articles
USRE43253E1 (en) 2005-03-22 2012-03-20 Nova Chemicals Inc. Lightweight concrete compositions
US8828170B2 (en) 2010-03-04 2014-09-09 Pactiv LLC Apparatus and method for manufacturing reinforced containers
US20150203649A1 (en) * 2014-01-23 2015-07-23 Sunbrite Packaging Company, Inc. Litter abatement with a photodegradable, single-use, foamed polystyrene packaging and container material and methods of making the same
US10006177B2 (en) 2015-09-23 2018-06-26 Nova Chemicals Inc. Workstation for flagman

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US3050476A (en) * 1958-12-08 1962-08-21 Koppers Co Inc Method of making a self extinguishing expandable polymer of styrene by bromination
US3039977A (en) * 1959-12-03 1962-06-19 Koppers Co Inc Method of producing self-extinguishing foamable polystyrene by brominating foamable polystyrene in aqueous suspension
US3088925A (en) * 1960-03-01 1963-05-07 Armstrong Cork Co Preparation of expandable polystyrene particles
DE1231424B (en) * 1961-05-27 1966-12-29 Basf Ag A process for the preparation of expandable molding compositions made from post-chlorinated polymers of vinyl chloride
US3800018A (en) * 1965-04-15 1974-03-26 Saint Gobain Fabrication of cellular resinous products

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US2435999A (en) * 1942-10-16 1948-02-17 Celanese Corp Process for the production of molding powder from a lower aliphatic ester of cellulose
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Cited By (83)

* Cited by examiner, † Cited by third party
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US3342760A (en) * 1961-10-26 1967-09-19 Koppers Co Inc Expandable polymers
US3178377A (en) * 1961-11-06 1965-04-13 Koppers Co Inc Expandable thermoplastic polymeric material
US3207712A (en) * 1961-12-08 1965-09-21 Koppers Co Inc Process for the production of expandable particles of styrene polymer
US3252228A (en) * 1962-04-23 1966-05-24 Lodge & Shipley Co Expander for polymeric material
US3250730A (en) * 1962-10-15 1966-05-10 Hercules Powder Co Ltd Preparation of molded plastic articles
US3305497A (en) * 1963-04-10 1967-02-21 Diamond Alkali Co Cellular polyurethanes produced using a mixture of (a) chloroform and (b) a fluorine substituted alkane as the blowing agent
US3386926A (en) * 1963-05-20 1968-06-04 Pechiney Saint Gobain Method of making expandable pearls of styrene copolymer
US3304274A (en) * 1963-06-13 1967-02-14 Union Carbide Corp Anhydrous process for the preparation of expandable particulate styrene polymers
US3359130A (en) * 1963-11-12 1967-12-19 Papex Corp Double shelled foamable plastic particles
US3331899A (en) * 1964-11-30 1967-07-18 Koppers Co Inc Process and apparatus for making shaped cellular articles from expandable thermoplastic resins
US3192169A (en) * 1965-01-07 1965-06-29 Kenneth W Doak Method of making expandable polymeric styrene particles
US3468820A (en) * 1965-01-16 1969-09-23 Basf Ag Production of particulate expandable styrene polymers
US3379799A (en) * 1965-10-20 1968-04-23 Papex Corp Method of making foamed plastics
US3494879A (en) * 1966-05-23 1970-02-10 Alfred J Ackerman Preparation of free-flowing foamable polystyrene beads
US3449268A (en) * 1966-05-31 1969-06-10 Dow Chemical Co Process for making foamable isotactic polystyrene
US3503908A (en) * 1967-07-31 1970-03-31 Koppers Co Inc Method of making expandable polymers
US3528433A (en) * 1968-03-21 1970-09-15 Philip Morris Inc Smoking product having microreticulated filter
US3449270A (en) * 1968-05-28 1969-06-10 Dow Chemical Co Method of making foamed crystalline vinyl aromatic polymer
US4018946A (en) * 1971-01-15 1977-04-19 Sealed Air Corporation Production of heat-expandable styrene-polymer bit-pieces
US3960787A (en) * 1971-10-25 1976-06-01 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparing foamable synthetic resin granules
US4207378A (en) * 1973-03-16 1980-06-10 Max Klein Expanded styrene-polymers and polyolefin micro-bits and their preparation
US4200679A (en) * 1973-03-16 1980-04-29 Max Klein Micro-bits of expanded flexible polyurethanes
US3917545A (en) * 1973-04-05 1975-11-04 Arco Polymers Inc Photodegradable styrene polymer foams containing a hydrocarbon photosensitizer
US3903024A (en) * 1973-10-19 1975-09-02 Arco Polymers Inc Photodegradable styrene polymer foams
US4304873A (en) * 1977-09-15 1981-12-08 Max Klein Preparation of expanded flexible polyurethane foam micro-bits
EP0518140A1 (en) 1991-05-31 1992-12-16 ENICHEM S.p.A. Process for producing foamable particles of styrenic polymers
US5308878A (en) * 1991-05-31 1994-05-03 Enichem S.P.A. Process for producing foamable particles of styrenic polymers, having improved processability and mechanical properties
US5939180A (en) * 1994-12-14 1999-08-17 Sekisui Kagaku Kogyo Kabushiki Kaisha Thermoplastic resin foam and method of preparing the same
US5960851A (en) * 1998-08-04 1999-10-05 Brunswick Corporation Method of lost foam casting of aluminum-silicon alloys
US6263950B1 (en) 1999-03-26 2001-07-24 General Motors Corporation Lost foam casting using dimensionally self-stabilized pattern
US20100088984A1 (en) * 2005-02-25 2010-04-15 Nova Chemicals Inc. Lightweight compositions and articles containing such
US20060201090A1 (en) * 2005-02-25 2006-09-14 Tricia Guevara Lightweight compositions and articles containing such
US7790302B2 (en) 2005-02-25 2010-09-07 Nova Chemicals Inc. Lightweight compositions and articles containing such
US8752348B2 (en) 2005-02-25 2014-06-17 Syntheon Inc. Composite pre-formed construction articles
US8726594B2 (en) 2005-02-25 2014-05-20 Syntheon Inc. Composite pre-formed building panels
US20060191232A1 (en) * 2005-02-25 2006-08-31 Nova Chemicals, Inc. Composite pre-formed building panels
US20110138725A1 (en) * 2005-02-25 2011-06-16 Nova Chemicals Inc. Composite pre-formed construction articles
US20080057290A1 (en) * 2005-02-25 2008-03-06 Nova Chemicals Inc. Lightweight compositions and articles containing such
US20110214391A1 (en) * 2005-02-25 2011-09-08 Nova Chemicals Inc. Lightweight compositions and articles containing such
US7964272B2 (en) 2005-02-25 2011-06-21 Nova Chemicals Inc. Lightweight compositions and articles containing such
US7963080B1 (en) 2005-02-25 2011-06-21 Nova Chemicals Inc. Composite pre-formed construction articles
US7666258B2 (en) 2005-02-25 2010-02-23 Nova Chemicals Inc. Lightweight compositions and articles containing such
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WO2006102523A2 (en) 2005-03-22 2006-09-28 Nova Chemicals Inc. Lightweight concrete compositions
US7699929B2 (en) 2005-03-22 2010-04-20 Nova Chemicals Inc. Lightweight concrete compositions
USRE43253E1 (en) 2005-03-22 2012-03-20 Nova Chemicals Inc. Lightweight concrete compositions
US20080314295A1 (en) * 2005-03-22 2008-12-25 Nova Chemicals Inc. Lightweight concrete compositions
US7704347B2 (en) 2005-05-27 2010-04-27 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US8087147B2 (en) 2005-05-27 2012-01-03 Prairie Packaging, Inc. Method of reinforcing a plastic foam cup
US20100323866A1 (en) * 2005-05-27 2010-12-23 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7818866B2 (en) 2005-05-27 2010-10-26 Prairie Packaging, Inc. Method of reinforcing a plastic foam cup
US7814647B2 (en) 2005-05-27 2010-10-19 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US8622208B2 (en) 2005-05-27 2014-01-07 Pactiv LLC Reinforced cup
US7694843B2 (en) 2005-05-27 2010-04-13 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7536767B2 (en) 2005-05-27 2009-05-26 Prairie Packaging, Inc. Method of manufacturing a reinforced plastic foam cup
US7918005B2 (en) 2005-05-27 2011-04-05 Prairie Packaging, Inc. Reinforced foam cup, method of and apparatus for manufacturing same
US7552841B2 (en) 2005-05-27 2009-06-30 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US7918016B2 (en) 2005-05-27 2011-04-05 Prairie Packaging, Inc. Reinforced plastic foam cup, method of and apparatus for manufacturing same
US20100047496A1 (en) * 2005-08-22 2010-02-25 Nova Chemicals Inc. Labeled containers, methods and devices for making same
US7628597B2 (en) 2005-08-22 2009-12-08 Nova Chemicals Inc. Labeled containers, methods and devices for making same
US20080020156A1 (en) * 2005-08-22 2008-01-24 Nova Chemicals Inc. Labeled containers, methods and devices for making same
US20070148386A1 (en) * 2005-12-22 2007-06-28 Nova Chemicals Inc. Method for improving the resistance of fumigant sorption in an expandable polymer produce container and a related container
US20070148385A1 (en) * 2005-12-22 2007-06-28 Nova Chemicals Inc. Methods for improving the resistance of fumigant sorption in a produce container and a related produce containers
US8101101B2 (en) 2005-12-22 2012-01-24 Nova Chemicals Inc. Methods for improving the resistance of fumigant sorption in a produce container and a related produce containers
US8101102B2 (en) 2005-12-22 2012-01-24 Nova Chemicals Inc. Method for improving the resistance of fumigant sorption in an expandable polymer produce container and a related container
WO2007111850A2 (en) 2006-03-22 2007-10-04 Nova Chemicals Inc. Lightweight concrete compositions
US20080250739A1 (en) * 2006-11-08 2008-10-16 Nova Chemicals Inc. Foamed plastic structures
US7677009B2 (en) 2007-02-02 2010-03-16 Nova Chemicals Inc. Roof truss system
US20080184651A1 (en) * 2007-02-02 2008-08-07 Bowman Jay J Roof truss system
US20080227891A1 (en) * 2007-03-14 2008-09-18 Nova Chemicals Inc. Methods for making concrete compositions
US20090011667A1 (en) * 2007-03-26 2009-01-08 Nova Chemicals Inc. Sportsboard structures
US20090081446A1 (en) * 2007-09-20 2009-03-26 Nova Chemicals Inc. Method of placing concrete
US20090078161A1 (en) * 2007-09-20 2009-03-26 Nova Chemicals Inc. Methods of minimizing concrete cracking and shrinkage
US8048219B2 (en) 2007-09-20 2011-11-01 Nova Chemicals Inc. Method of placing concrete
US8114492B2 (en) 2007-12-19 2012-02-14 Nova Chemicals Inc. Labeled containers made from expandable thermoplastic materials having improved physical properties
US20090162588A1 (en) * 2007-12-19 2009-06-25 Nova Chemicals Inc. Labeled containers made from expandable thermoplastic materials having improved physical properties
US20090313914A1 (en) * 2008-06-20 2009-12-24 Nova Chemicals, Inc.. Footer cleat for insulating concrete form
US7874112B2 (en) 2008-06-20 2011-01-25 Nova Chemicals Inc. Footer cleat for insulating concrete form
US8828170B2 (en) 2010-03-04 2014-09-09 Pactiv LLC Apparatus and method for manufacturing reinforced containers
US9676141B2 (en) 2010-03-04 2017-06-13 Pactiv LLC Apparatus and method for manufacturing reinforced containers
US20150203649A1 (en) * 2014-01-23 2015-07-23 Sunbrite Packaging Company, Inc. Litter abatement with a photodegradable, single-use, foamed polystyrene packaging and container material and methods of making the same
US10246839B2 (en) 2015-09-23 2019-04-02 Nova Chemicals Inc. Workstation for flagman
US10006177B2 (en) 2015-09-23 2018-06-26 Nova Chemicals Inc. Workstation for flagman

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FR1113827A (en) 1956-04-04
CH332147A (en) 1958-08-31
GB756654A (en) 1956-09-05
BE532626A (en)
ES218623A1 (en) 1955-12-01

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